Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801016774/na6103sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801016774/na6103Isup2.hkl |
CCDC reference: 176013
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.011 Å
- Disorder in main residue
- R factor = 0.088
- wR factor = 0.226
- Data-to-parameter ratio = 12.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
PLAT_305 Alert A Isolated Hydrogen Atom (Outside Bond Range ??)
Author response: There is no isolated hydrogen atom. PLAT_305 Alert A Isolated Hydrogen Atom (Outside Bond Range ??)
Author response: There is no isolated hydrogen atom. PLAT_305 Alert A Isolated Hydrogen Atom (Outside Bond Range ??)
Author response: There is no isolated hydrogen atom.
Alert Level C:
PLAT_301 Alert C Main Residue Disorder ........................ 7.00 Perc.
3 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
A solution of 0.98 M methyl lithium (1.10 ml, 0.99 mmol), which was freshly prepared from methyl iodide and lithium, was added to a cool solution of methyl 4-(2-carboxy-3,5-methoxy-6-methylphenoxy)-2,6-dihydroxy-3-methylbenzoate (39 mg, 0.01 mmol) in dry tetrahydrofuran (5 ml) under a nitrogen atmosphere. The reaction mixture was stirred at 273 K for 3 h and an for an additional 6 h at room temperature. Saturated ammonium chloride (30 ml) was then added to the solution. The resulting mixture was extracted with ether. After extraction, the solvent was removed in vacuo and the crude product was purified by preparative thin-layer chromatography with 20% hexane/chloroform as eluent to give a brown solid which was recrystallized from chloroform.
After checking their presence in the difference map, all H atoms were geometrically fixed and allowed to ride on the atoms to which they were attached, with Uiso = 1.2Ueq for aromatic parent atoms and 1.5Ueq for methyl C atoms and hydroxyl O atoms, and with –C–H = 0.96 Å and O—H = 0.82 Å. Due to a large fraction of weak data at higher angles, the 2θ maximum was limited to 50°. Even with this limitation, the coverage of the unit set is only 93.2% complete because the crystal is not very reflecting and there is disorder in the structure.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 1990).
C18H19IO7 | Z = 2 |
Mr = 474.23 | F(000) = 472 |
Triclinic, P1 | Dx = 1.688 Mg m−3 |
a = 8.8878 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.6008 (2) Å | Cell parameters from 3302 reflections |
c = 11.2792 (3) Å | θ = 2.0–25.0° |
α = 62.253 (1)° | µ = 1.75 mm−1 |
β = 87.872 (1)° | T = 293 K |
γ = 82.953 (1)° | Block, brown |
V = 933.16 (4) Å3 | 0.36 × 0.24 × 0.18 mm |
Siemens SMART CCD area-detector diffractometer | 3302 independent reflections |
Radiation source: fine-focus sealed tube | 2039 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.081 |
Detector resolution: 8.33 pixels mm-1 | θmax = 25.0°, θmin = 2.0° |
ω scans | h = −7→10 |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | k = −10→12 |
Tmin = 0.571, Tmax = 0.743 | l = −10→13 |
5044 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.088 | H-atom parameters constrained |
wR(F2) = 0.226 | w = 1/[σ2(Fo2) + (0.1141P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.98 | (Δ/σ)max < 0.001 |
3078 reflections | Δρmax = 1.46 e Å−3 |
250 parameters | Δρmin = −0.65 e Å−3 |
4 restraints | Extinction correction: SHELXTL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.098 (11) |
C18H19IO7 | γ = 82.953 (1)° |
Mr = 474.23 | V = 933.16 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.8878 (3) Å | Mo Kα radiation |
b = 10.6008 (2) Å | µ = 1.75 mm−1 |
c = 11.2792 (3) Å | T = 293 K |
α = 62.253 (1)° | 0.36 × 0.24 × 0.18 mm |
β = 87.872 (1)° |
Siemens SMART CCD area-detector diffractometer | 3302 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2039 reflections with I > 2σ(I) |
Tmin = 0.571, Tmax = 0.743 | Rint = 0.081 |
5044 measured reflections |
R[F2 > 2σ(F2)] = 0.088 | 4 restraints |
wR(F2) = 0.226 | H-atom parameters constrained |
S = 0.98 | Δρmax = 1.46 e Å−3 |
3078 reflections | Δρmin = −0.65 e Å−3 |
250 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0,88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 4.023 cm and the detector swing angle was -35°. Crystal decay was monitored by SAINT (Siemens, 1996) and was found to be negligible. |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
I/CA | 0.95733 (11) | 0.34053 (11) | 0.19968 (10) | 0.0688 (5) | 0.569 (4) |
C18A | 1.349 (3) | −0.115 (2) | 0.235 (2) | 0.0658 (6) | 0.569 (4) |
H18A | 1.2741 | −0.1285 | 0.1841 | 0.099* | 0.569 (4) |
H18B | 1.3923 | −0.2062 | 0.3036 | 0.099* | 0.569 (4) |
H18C | 1.4279 | −0.0668 | 0.1759 | 0.099* | 0.569 (4) |
I/CB | 1.37477 (17) | −0.13760 (17) | 0.20670 (16) | 0.0658 (6) | 0.43 |
C18B | 1.023 (3) | 0.3084 (18) | 0.210 (2) | 0.0688 (5) | 0.43 |
H18E | 0.9580 | 0.3371 | 0.2648 | 0.103* | 0.431 (4) |
H18F | 0.9629 | 0.3015 | 0.1445 | 0.103* | 0.431 (4) |
H18G | 1.0922 | 0.3783 | 0.1647 | 0.103* | 0.431 (4) |
O1 | 1.1253 (6) | 0.1309 (6) | 0.1016 (5) | 0.0604 (15) | |
O2 | 1.2331 (6) | 0.0068 (6) | 0.7032 (6) | 0.0684 (16) | |
O3 | 1.4130 (7) | −0.1511 (7) | 0.6924 (6) | 0.0780 (18) | |
O4 | 1.0851 (7) | 0.2005 (7) | 0.4884 (6) | 0.0773 (17) | |
H4A | 1.1112 | 0.1647 | 0.5675 | 0.116* | |
O5 | 1.4334 (7) | −0.1871 (6) | 0.4849 (6) | 0.0739 (17) | |
H5A | 1.4527 | −0.2014 | 0.5610 | 0.111* | |
O6 | 1.5512 (6) | 0.3868 (6) | −0.0681 (6) | 0.0685 (16) | |
O7 | 1.1531 (7) | 0.4092 (7) | −0.3599 (5) | 0.0795 (19) | |
C1 | 1.3417 (8) | 0.2638 (8) | 0.0172 (7) | 0.0517 (17) | |
H1A | 1.3817 | 0.2279 | 0.1034 | 0.062* | |
C2 | 1.4172 (8) | 0.3582 (8) | −0.0945 (7) | 0.0509 (18) | |
C3 | 1.3561 (8) | 0.4090 (7) | −0.2229 (6) | 0.054 (2) | |
H3A | 1.4055 | 0.4714 | −0.2976 | 0.065* | |
C4 | 1.2222 (8) | 0.3654 (8) | −0.2373 (7) | 0.0507 (18) | |
C5 | 1.1380 (8) | 0.2728 (8) | −0.1283 (7) | 0.0524 (18) | |
C6 | 1.2067 (8) | 0.2257 (7) | −0.0042 (7) | 0.0490 (17) | |
C7 | 1.1746 (8) | 0.0907 (8) | 0.2352 (7) | 0.0548 (19) | |
C8 | 1.1092 (8) | 0.1682 (7) | 0.2937 (7) | 0.058 (2) | |
C9 | 1.1534 (9) | 0.1181 (9) | 0.4334 (8) | 0.0570 (19) | |
C10 | 1.2600 (8) | 0.0017 (8) | 0.4966 (7) | 0.0520 (18) | |
C11 | 1.3229 (8) | −0.0736 (8) | 0.4274 (8) | 0.0520 (18) | |
C12 | 1.2794 (8) | −0.0278 (7) | 0.2948 (6) | 0.0534 (18) | |
C13 | 1.3094 (9) | −0.0567 (9) | 0.6404 (8) | 0.060 (2) | |
C14 | 0.9917 (9) | 0.2348 (9) | −0.1461 (8) | 0.067 (2) | |
H14A | 0.9802 | 0.2522 | −0.2369 | 0.100* | |
H14B | 0.9122 | 0.2922 | −0.1269 | 0.100* | |
H14C | 0.9862 | 0.1351 | −0.0863 | 0.100* | |
C15 | 1.6214 (10) | 0.5009 (9) | −0.1677 (9) | 0.068 (2) | |
H15A | 1.7093 | 0.5143 | −0.1300 | 0.102* | |
H15B | 1.5515 | 0.5872 | −0.2018 | 0.102* | |
H15C | 1.6511 | 0.4789 | −0.2394 | 0.102* | |
C16 | 1.2671 (12) | −0.0555 (12) | 0.8457 (9) | 0.083 (3) | |
H16A | 1.2068 | −0.0011 | 0.8824 | 0.125* | |
H16B | 1.3727 | −0.0536 | 0.8591 | 0.125* | |
H16C | 1.2443 | −0.1530 | 0.8897 | 0.125* | |
C17 | 1.2270 (12) | 0.5081 (15) | −0.4799 (9) | 0.105 (4) | |
H17A | 1.1752 | 0.5201 | −0.5583 | 0.157* | |
H17B | 1.3308 | 0.4696 | −0.4793 | 0.157* | |
H17C | 1.2236 | 0.5994 | −0.4808 | 0.157* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I/CA | 0.0664 (8) | 0.0533 (7) | 0.0610 (7) | 0.0064 (4) | −0.0118 (5) | −0.0072 (4) |
C18A | 0.0814 (11) | 0.0652 (9) | 0.0658 (10) | −0.0207 (7) | 0.0150 (7) | −0.0413 (7) |
I/CB | 0.0814 (11) | 0.0652 (9) | 0.0658 (10) | −0.0207 (7) | 0.0150 (7) | −0.0413 (7) |
C18B | 0.0664 (8) | 0.0533 (7) | 0.0610 (7) | 0.0064 (4) | −0.0118 (5) | −0.0072 (4) |
O1 | 0.060 (3) | 0.074 (3) | 0.029 (3) | −0.028 (3) | −0.001 (2) | −0.004 (2) |
O2 | 0.080 (4) | 0.071 (4) | 0.042 (3) | −0.008 (3) | 0.003 (2) | −0.016 (3) |
O3 | 0.089 (4) | 0.073 (4) | 0.046 (3) | −0.004 (3) | −0.008 (3) | −0.006 (3) |
O4 | 0.096 (4) | 0.079 (4) | 0.053 (4) | 0.016 (3) | −0.009 (3) | −0.033 (3) |
O5 | 0.087 (4) | 0.053 (3) | 0.058 (4) | 0.006 (3) | −0.014 (3) | −0.008 (3) |
O6 | 0.066 (4) | 0.063 (4) | 0.055 (3) | −0.023 (3) | −0.007 (2) | −0.006 (3) |
O7 | 0.085 (4) | 0.099 (5) | 0.023 (3) | −0.023 (3) | −0.003 (2) | 0.001 (3) |
C1 | 0.064 (5) | 0.048 (4) | 0.032 (4) | −0.011 (3) | −0.004 (3) | −0.008 (3) |
C2 | 0.040 (4) | 0.055 (4) | 0.047 (4) | −0.014 (3) | 0.004 (3) | −0.013 (3) |
C3 | 0.066 (5) | 0.052 (4) | 0.025 (3) | −0.005 (3) | 0.008 (3) | −0.003 (3) |
C4 | 0.050 (4) | 0.054 (4) | 0.034 (4) | −0.010 (3) | 0.001 (3) | −0.007 (3) |
C5 | 0.053 (4) | 0.050 (4) | 0.042 (4) | −0.005 (3) | 0.003 (3) | −0.012 (3) |
C6 | 0.056 (5) | 0.042 (4) | 0.031 (3) | −0.012 (3) | 0.002 (3) | −0.001 (3) |
C7 | 0.062 (5) | 0.057 (5) | 0.033 (4) | −0.027 (4) | 0.000 (3) | −0.005 (3) |
C8 | 0.065 (5) | 0.052 (4) | 0.040 (4) | −0.011 (3) | 0.001 (3) | −0.007 (3) |
C9 | 0.064 (5) | 0.060 (5) | 0.043 (4) | −0.011 (4) | 0.001 (3) | −0.018 (3) |
C10 | 0.056 (4) | 0.050 (4) | 0.032 (4) | −0.018 (3) | 0.002 (3) | −0.002 (3) |
C11 | 0.044 (4) | 0.049 (4) | 0.055 (5) | −0.008 (3) | 0.001 (3) | −0.017 (3) |
C12 | 0.064 (5) | 0.052 (4) | 0.030 (4) | −0.017 (3) | 0.005 (3) | −0.005 (3) |
C13 | 0.061 (5) | 0.058 (5) | 0.043 (4) | −0.014 (4) | −0.001 (3) | −0.008 (4) |
C14 | 0.070 (5) | 0.066 (5) | 0.044 (4) | −0.018 (4) | −0.004 (3) | −0.006 (3) |
C15 | 0.073 (5) | 0.057 (5) | 0.064 (5) | −0.035 (4) | 0.020 (4) | −0.015 (4) |
C16 | 0.088 (7) | 0.097 (7) | 0.043 (5) | −0.013 (5) | −0.006 (4) | −0.014 (4) |
C17 | 0.104 (8) | 0.154 (11) | 0.033 (5) | −0.055 (7) | 0.007 (4) | −0.014 (5) |
I/CA—C8 | 1.995 (6) | C2—C3 | 1.394 (10) |
C18A—C12 | 1.452 (9) | C3—C4 | 1.369 (10) |
C18A—H18A | 0.9600 | C3—H3A | 0.9300 |
C18A—H18B | 0.9600 | C4—C5 | 1.422 (10) |
C18A—H18C | 0.9600 | C5—C6 | 1.385 (10) |
I/CB—C12 | 1.958 (6) | C5—C14 | 1.455 (11) |
C18B—C8 | 1.468 (10) | C7—C8 | 1.345 (11) |
C18B—H18E | 0.9600 | C7—C12 | 1.368 (10) |
C18B—H18F | 0.9600 | C8—C9 | 1.461 (11) |
C18B—H18G | 0.9600 | C9—C10 | 1.368 (11) |
O1—C6 | 1.398 (8) | C10—C11 | 1.414 (11) |
O1—C7 | 1.431 (8) | C10—C13 | 1.503 (10) |
O2—C13 | 1.308 (10) | C11—C12 | 1.394 (10) |
O2—C16 | 1.452 (10) | C14—H14A | 0.9600 |
O3—C13 | 1.209 (10) | C14—H14B | 0.9600 |
O4—C9 | 1.365 (10) | C14—H14C | 0.9600 |
O4—H4A | 0.8200 | C15—H15A | 0.9600 |
O5—C11 | 1.365 (9) | C15—H15B | 0.9600 |
O5—H5A | 0.8200 | C15—H15C | 0.9600 |
O6—C2 | 1.341 (9) | C16—H16A | 0.9600 |
O6—C15 | 1.407 (9) | C16—H16B | 0.9600 |
O7—C4 | 1.379 (9) | C16—H16C | 0.9600 |
O7—C17 | 1.465 (11) | C17—H17A | 0.9600 |
C1—C6 | 1.376 (10) | C17—H17B | 0.9600 |
C1—C2 | 1.402 (10) | C17—H17C | 0.9600 |
C1—H1A | 0.9300 | ||
C12—C18A—H18A | 109.5 | O4—C9—C10 | 125.2 (7) |
C12—C18A—H18B | 109.5 | O4—C9—C8 | 114.2 (7) |
C12—C18A—H18C | 109.5 | C10—C9—C8 | 120.5 (7) |
C8—C18B—H18E | 109.5 | C9—C10—C11 | 119.5 (7) |
C8—C18B—H18F | 109.5 | C9—C10—C13 | 123.3 (7) |
H18E—C18B—H18F | 109.5 | C11—C10—C13 | 117.2 (7) |
C8—C18B—H18G | 109.5 | O5—C11—C12 | 118.2 (7) |
H18E—C18B—H18G | 109.5 | O5—C11—C10 | 121.4 (7) |
H18F—C18B—H18G | 109.5 | C12—C11—C10 | 120.3 (6) |
C6—O1—C7 | 117.7 (5) | C7—C12—C11 | 118.0 (6) |
C13—O2—C16 | 115.6 (7) | C7—C12—C18A | 126.4 (12) |
C9—O4—H4A | 109.5 | C11—C12—C18A | 115.5 (12) |
C11—O5—H5A | 109.5 | C7—C12—I/CB | 124.7 (5) |
C2—O6—C15 | 119.9 (6) | C11—C12—I/CB | 117.3 (5) |
C4—O7—C17 | 117.8 (7) | C18A—C12—I/CB | 2.4 (10) |
C6—C1—C2 | 118.2 (6) | O3—C13—O2 | 123.0 (8) |
C6—C1—H1A | 120.9 | O3—C13—C10 | 123.0 (8) |
C2—C1—H1A | 120.9 | O2—C13—C10 | 113.9 (7) |
O6—C2—C3 | 124.4 (6) | C5—C14—H14A | 109.5 |
O6—C2—C1 | 115.6 (7) | C5—C14—H14B | 109.5 |
C3—C2—C1 | 119.9 (7) | H14A—C14—H14B | 109.5 |
C4—C3—C2 | 118.9 (6) | C5—C14—H14C | 109.5 |
C4—C3—H3A | 120.5 | H14A—C14—H14C | 109.5 |
C2—C3—H3A | 120.5 | H14B—C14—H14C | 109.5 |
C3—C4—O7 | 123.3 (6) | O6—C15—H15A | 109.5 |
C3—C4—C5 | 124.0 (7) | O6—C15—H15B | 109.5 |
O7—C4—C5 | 112.7 (7) | H15A—C15—H15B | 109.5 |
C6—C5—C4 | 113.6 (7) | O6—C15—H15C | 109.5 |
C6—C5—C14 | 123.5 (7) | H15A—C15—H15C | 109.5 |
C4—C5—C14 | 122.9 (7) | H15B—C15—H15C | 109.5 |
C1—C6—C5 | 125.3 (6) | O2—C16—H16A | 109.5 |
C1—C6—O1 | 121.7 (6) | O2—C16—H16B | 109.5 |
C5—C6—O1 | 113.0 (6) | H16A—C16—H16B | 109.5 |
C8—C7—C12 | 125.5 (7) | O2—C16—H16C | 109.5 |
C8—C7—O1 | 117.5 (7) | H16A—C16—H16C | 109.5 |
C12—C7—O1 | 117.0 (7) | H16B—C16—H16C | 109.5 |
C7—C8—C9 | 116.2 (6) | O7—C17—H17A | 109.5 |
C7—C8—C18B | 118.9 (13) | O7—C17—H17B | 109.5 |
C9—C8—C18B | 123.9 (13) | H17A—C17—H17B | 109.5 |
C7—C8—I/CA | 123.1 (6) | O7—C17—H17C | 109.5 |
C9—C8—I/CA | 120.7 (6) | H17A—C17—H17C | 109.5 |
C18B—C8—I/CA | 11.3 (11) | H17B—C17—H17C | 109.5 |
C15—O6—C2—C3 | 16.6 (12) | C18B—C8—C9—O4 | 11.4 (17) |
C15—O6—C2—C1 | −167.2 (7) | I/CA—C8—C9—O4 | −1.4 (9) |
C6—C1—C2—O6 | −177.3 (6) | C7—C8—C9—C10 | 2.4 (11) |
C6—C1—C2—C3 | −0.9 (11) | C18B—C8—C9—C10 | −165.8 (15) |
O6—C2—C3—C4 | 176.2 (7) | I/CA—C8—C9—C10 | −178.6 (6) |
C1—C2—C3—C4 | 0.2 (11) | O4—C9—C10—C11 | −179.4 (7) |
C2—C3—C4—O7 | −179.8 (7) | C8—C9—C10—C11 | −2.6 (11) |
C2—C3—C4—C5 | 1.5 (11) | O4—C9—C10—C13 | 3.9 (12) |
C17—O7—C4—C3 | −0.5 (13) | C8—C9—C10—C13 | −179.2 (7) |
C17—O7—C4—C5 | 178.4 (9) | C9—C10—C11—O5 | 177.6 (7) |
C3—C4—C5—C6 | −2.1 (11) | C13—C10—C11—O5 | −5.5 (10) |
O7—C4—C5—C6 | 179.0 (7) | C9—C10—C11—C12 | 1.5 (11) |
C3—C4—C5—C14 | 176.4 (8) | C13—C10—C11—C12 | 178.4 (7) |
O7—C4—C5—C14 | −2.5 (11) | C8—C7—C12—C11 | 0.2 (11) |
C2—C1—C6—C5 | 0.1 (12) | O1—C7—C12—C11 | −176.5 (6) |
C2—C1—C6—O1 | 179.3 (7) | C8—C7—C12—C18A | 178.7 (13) |
C4—C5—C6—C1 | 1.3 (11) | O1—C7—C12—C18A | 2.0 (15) |
C14—C5—C6—C1 | −177.2 (8) | C8—C7—C12—I/CB | −179.3 (6) |
C4—C5—C6—O1 | −177.9 (6) | O1—C7—C12—I/CB | 4.0 (9) |
C14—C5—C6—O1 | 3.6 (11) | O5—C11—C12—C7 | −176.5 (7) |
C7—O1—C6—C1 | 9.1 (11) | C10—C11—C12—C7 | −0.3 (10) |
C7—O1—C6—C5 | −171.7 (7) | O5—C11—C12—C18A | 4.8 (14) |
C6—O1—C7—C8 | 93.2 (8) | C10—C11—C12—C18A | −179.0 (12) |
C6—O1—C7—C12 | −89.8 (8) | O5—C11—C12—I/CB | 3.0 (9) |
C12—C7—C8—C9 | −1.2 (11) | C10—C11—C12—I/CB | 179.2 (5) |
O1—C7—C8—C9 | 175.5 (6) | C16—O2—C13—O3 | −7.7 (12) |
C12—C7—C8—C18B | 167.6 (14) | C16—O2—C13—C10 | 174.2 (7) |
O1—C7—C8—C18B | −15.7 (16) | C9—C10—C13—O3 | −173.1 (8) |
C12—C7—C8—I/CA | 179.8 (6) | C11—C10—C13—O3 | 10.2 (11) |
O1—C7—C8—I/CA | −3.5 (9) | C9—C10—C13—O2 | 5.0 (11) |
C7—C8—C9—O4 | 179.6 (7) | C11—C10—C13—O2 | −171.8 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O2 | 0.82 | 1.90 | 2.600 (9) | 143 |
O5—H5A···O3 | 0.82 | 1.80 | 2.538 (9) | 148 |
Experimental details
Crystal data | |
Chemical formula | C18H19IO7 |
Mr | 474.23 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 8.8878 (3), 10.6008 (2), 11.2792 (3) |
α, β, γ (°) | 62.253 (1), 87.872 (1), 82.953 (1) |
V (Å3) | 933.16 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.75 |
Crystal size (mm) | 0.36 × 0.24 × 0.18 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.571, 0.743 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5044, 3302, 2039 |
Rint | 0.081 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.088, 0.226, 0.98 |
No. of reflections | 3078 |
No. of parameters | 250 |
No. of restraints | 4 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.46, −0.65 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL and PLATON (Spek, 1990).
I/CA—C8 | 1.995 (6) | I/CB—C12 | 1.958 (6) |
C18A—C12 | 1.452 (9) | C18B—C8 | 1.468 (10) |
C6—O1—C7 | 117.7 (5) | ||
C15—O6—C2—C3 | 16.6 (12) | C8—C7—C12—C18A | 178.7 (13) |
C6—C1—C2—O6 | −177.3 (6) | C8—C7—C12—I/CB | −179.3 (6) |
C14—C5—C6—C1 | −177.2 (8) | C16—O2—C13—C10 | 174.2 (7) |
I/CA—C8—C9—C10 | −178.6 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4A···O2 | 0.82 | 1.90 | 2.600 (9) | 143 |
O5—H5A···O3 | 0.82 | 1.80 | 2.538 (9) | 148 |
The diphenyl ethers could be prepared readily by the convertion of p-depsides which are produced from a wide variety of metabolites of lichen (Elix et al., 1978) and by synthesis (Elix & Jenie, 1989; Chantrapromma et al., 1998) via an intramolecular Smiles rearrangement (Elix et al., 1984). Suitable reaction conditions for an intramolecular Smiles rearrangement of the prepared depsides have also been studied extensively (Elix & Jenie, 1989; Elix et al., 1990). In previous work, we have reported the structure of diphenyl ethers by intramolecular Smiles rearrangement of the prepared corresponding depsides (Chantrapromma et al., 2000; Karalai et al., 2001). Structure determinations were undertaken as part of our structural studies on diphenyl ether derivatives. The title compound, (I), was unexpectedly obtained upon treatment of methyl 4-(2-carboxy-3,5-methoxy-6-methylphenoxy)-2,6-dihydroxy-3-methylbenzoate with excess of methyl lithium (freshly prepared from methyl iodide and lithium), instead of the expected product, the 2-acetylphenoxy analog of the starting material. It is quite hard to get a good quality crystal of the title compound.
A displacement ellipsoid plot with the atomic numbering scheme of the title compound is shown in Fig. 1. The observed molecule is disordered into two conformations, one related to the other by rotation of the 2,6-dihydroxy-3-iodo-5-methylbenzoate moiety about the O—C central bond joining it to the phenoxy residue, by 180°. Disorder is such as to have only 3- and 5-positions of phenyl occupied alternatively by the iodine and methyl group. The bond lengths and angles observed in the structure are normal and agree with reported values (Allen et al., 1987; Chantrapromma et al., 1998, 2000; Karalai et al., 2001). The two benzene rings are nearly perpendicular to each other [dihedral angle 83.0 (4)°]. One methoxy group is coplanar with the attached benzene ring [C17—O7—C4—C3 = -0.5 (13)°] but the other is twisted out of the benzene ring [C15—O6—C2—C3 = 16.6 (12)°], while the carbomethoxy group is nearly coplanar with the attached benzene rings [C16—O2—C13—C10 = 174.2 (3)°]. The hydroxyl groups in the molecule are involved in intramolecular O—H···O hydrogen bonds with the carbomethoxy O atoms (Table 2), whereas the O atom of methoxy group is involved in a weak intramolecular C14—H14A···O7 interaction (H14A···O7 = 2.32 Å and C14—H14A···O7 = 106°). The crystal structure is stabilized by these intramolecular O—H···O hydrogen bonds and weak C—H···O interactions. The molecules are stacked on top of one another along the a axis (Fig. 2).